EP1442010B1 - Method for the production of biphenyl-4-carbonitrile - Google Patents
Method for the production of biphenyl-4-carbonitrile Download PDFInfo
- Publication number
- EP1442010B1 EP1442010B1 EP02783019A EP02783019A EP1442010B1 EP 1442010 B1 EP1442010 B1 EP 1442010B1 EP 02783019 A EP02783019 A EP 02783019A EP 02783019 A EP02783019 A EP 02783019A EP 1442010 B1 EP1442010 B1 EP 1442010B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- biphenyl
- carbonitrile
- chlorobenzene
- mol
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical compound C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 12
- 239000004305 biphenyl Substances 0.000 claims abstract description 11
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- -1 des Halogens Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
Definitions
- the present invention relates to a process for the preparation of biphenyl-4-carbonitrile of the formula
- Biphenyl-4-carbonitrile is an important intermediate, for example in the synthesis of pharmaceutical agents (see eg. WO-A-01/22951 ).
- DE-A-19833409 discloses a process for the production of biphenyl-4-carbonitrile by Friedel-Crafts acylation of 4-hydroxybiphenyl.
- the object of the present invention was to provide a process for the preparation of biphenyl-4-carbonitrile, which requires only inexpensive and available in large quantities starting materials and does not provide problematic waste. According to the invention this object is achieved by the method according to claim 1.
- the anhydrous aluminum chloride and the cyanogen chloride are preferably used in an amount of 1.0 to 1.5 moles to 1 mole of biphenyl, respectively.
- the inventive method is conveniently carried out in an inert solvent.
- an inert solvent This is understood to mean any solvent which does not react or reacts much slower than biphenyl under the reaction conditions.
- halogenated aromatic solvents for example chlorobenzene, bromobenzene or dichlorobenzenes. Particularly preferred is chlorobenzene.
- the inventive method is advantageously carried out at reaction temperatures of about 60 to 130 ° C.
- the reaction can be carried out in various ways, for example the biphenyl can be initially charged and then the aluminum chloride first and then the cyanogen chloride added. However, it is also possible to initially introduce the aluminum chloride and then first to introduce the cyanogen chloride and finally to add the biphenyl.
- the workup can be carried out in the manner customary for Friedel-Crafts reactions with aluminum chloride, for example by dissolving the aluminum salts in a large amount of acid and thus bringing them into the aqueous phase or precipitating them with a little water and filtering off.
- the reaction vessel was rinsed with 100 ml of chlorobenzene and the phases were separated. After draining the aqueous phase, the organic phase was washed at 90 ° C with 200 ml of water. The resulting organic phase was then stirred at 40 ° C with 5 g of activated carbon for 30 min and then filtered. Subsequently, the organic phase was evaporated to dryness. After drying at 50 ° C./10 mbar, 57.2 g (98.5%) of a yellow solid were obtained which, according to quantitative 13 C NMR analysis, contained about 80% of biphenyl-4-carbonitrile.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Biphenyl-4-carbonitril der Formel
Biphenyl-4-carbonitril ist ein wichtiges Zwischenprodukt, beispielsweise in der Synthese von pharmazeutischen Wirkstoffen (siehe z. B.
Es sind zahlreiche Verfahren zur Herstellung von Biphenyl-4-carbonitril bekannt. Diese lassen sich im wesentlichen in drei Kategorien einordnen:
- 1. Austausch des Halogens in 4-Halobiphenylen gegen die Cyanogruppe
- 2. Umwandlung der funktionellen Gruppe in 4-substituierten Biphenylen in die Cyanogruppe
- 3. Kupplung von p-substituierten Benzonitrilen mit Phenylverbindungen
- 1. Exchange of the halogen in 4-halobiphenylene for the cyano group
- 2. Conversion of the functional group in 4-substituted biphenyls into the cyano group
- 3. Coupling of p-substituted benzonitriles with phenyl compounds
Diese Verfahren besitzen den Nachteil, dass sie teure Ausgangsmaterialien und/oder Reagenzien erfordern, die nicht in grossen Mengen verfügbar sind, und teilweise grosse Mengen schwermetallhaltiger Abfälle produzieren. Ausserdem liefern sie teilweise keine reinen Produkte, so ist beispielsweise ein in Kleinmengen kommerziell erhältliches Biphenyl-4-carbonitril (Aldrich) mit ca. 5% der Bromverbindung verunreinigt.These processes have the disadvantage that they require expensive starting materials and / or reagents that are not available in large quantities, and sometimes produce large amounts of heavy metal-containing wastes. In addition, they sometimes do not provide pure products, for example, a commercially available in small quantities biphenyl-4-carbonitrile (Aldrich) is contaminated with about 5% of the bromine compound.
Aufgabe der vorliegenden Erfindung war es, ein Verfahren zur Herstellung von Biphenyl-4-carbonitril bereitzustellen, welches nur preiswerte und in grossen Mengen verfügbare Ausgangsmaterialien erfordert und keine problematischen Abfälle liefert. Erfindungsgemäss wird diese Aufgabe durch das Verfahren nach Patentanspruch 1 gelöst.The object of the present invention was to provide a process for the preparation of biphenyl-4-carbonitrile, which requires only inexpensive and available in large quantities starting materials and does not provide problematic waste. According to the invention this object is achieved by the method according to claim 1.
Es wurde überraschend gefunden, dass das in grossen Mengen verfügbare Biphenyl in Gegenwart von wasserfreiem Aluminiumchlorid mit Chlorcyan in guter Ausbeute und ohne nennenswerte Bildung von isomeren oder mehrfach cyanierten Nebenprodukten direkt zu dem gewünschten Biphenyl-4-carbonitril umgesetzt werden kann.It was surprisingly found that the available in large quantities biphenyl in the presence of anhydrous aluminum chloride with cyanogen chloride in good yield and can be reacted directly to the desired biphenyl-4-carbonitrile without appreciable formation of isomeric or poly-cyanated by-products.
Das wasserfreie Aluminiumchlorid und das Chlorcyan werden vorzugsweise in einer Menge von jeweils 1,0 bis 1,5 mol auf 1 mol Biphenyl eingesetzt.The anhydrous aluminum chloride and the cyanogen chloride are preferably used in an amount of 1.0 to 1.5 moles to 1 mole of biphenyl, respectively.
Das erfindungsgemässe Verfahren wird zweckmässig in einem inerten Lösungsmittel durchgeführt. Hierunter ist jedes Lösungsmittel zu verstehen, das unter den Reaktionsbedingungen nicht oder wesentlich langsamer als Biphenyl reagiert.
Vorzugsweise werden halogenierte aromatische Lösungsmittel wie beispielsweise Chlorbenzol, Brombenzol oder Dichlorbenzole eingesetzt. Besonders bevorzugt ist Chlorbenzol.The inventive method is conveniently carried out in an inert solvent. This is understood to mean any solvent which does not react or reacts much slower than biphenyl under the reaction conditions.
Preference is given to using halogenated aromatic solvents, for example chlorobenzene, bromobenzene or dichlorobenzenes. Particularly preferred is chlorobenzene.
Das erfindungsgemässe Verfahren wird vorteilhaft bei Reaktionstemperaturen von ca. 60 bis 130 °C durchgeführt.The inventive method is advantageously carried out at reaction temperatures of about 60 to 130 ° C.
Die Reaktion kann auf verschiedene Weisen durchgeführt werden, beispielsweise kann das Biphenyl vorgelegt und dann zuerst das Aluminiumchlorid und dann das Chlorcyan zugegeben werden. Es ist aber auch möglich, das Aluminiumchlorid vorzulegen und dann zuerst das Chlorcyan einzuleiten und zuletzt das Biphenyl zuzugeben.The reaction can be carried out in various ways, for example the biphenyl can be initially charged and then the aluminum chloride first and then the cyanogen chloride added. However, it is also possible to initially introduce the aluminum chloride and then first to introduce the cyanogen chloride and finally to add the biphenyl.
Die Aufarbeitung kann in der für Friedel-Crafts-Reaktionen mit Aluminiumchlorid üblichen Weise erfolgen, beispielsweise indem die Aluminiumsalze in viel Säure aufgelöst und so in die wässrige Phase gebracht oder mit wenig Wasser ausgefällt und abfiltriert werden.The workup can be carried out in the manner customary for Friedel-Crafts reactions with aluminum chloride, for example by dissolving the aluminum salts in a large amount of acid and thus bringing them into the aqueous phase or precipitating them with a little water and filtering off.
Die folgenden Beispiele verdeutlichen die Durchführung des erfindungsgemässen Verfahrens, ohne dass darin eine Einschränkung zu sehen ist.The following examples illustrate the implementation of the method according to the invention, without any restriction being given therein.
In 200 ml Chlorbenzol wurden bei 25 °C unter Stickstoff 50 g (0,324 mol) Biphenyl gelöst. Anschliessend wurden 51,88 g (0,389 mol) wasserfreies Aluminiumchlorid zugegeben und für 15 min gerührt. Bei 20-25 °C wurden darauf 23,92 g (0,389 mol) Chlorcyan innerhalb einer Stunde eingeleitet. Nach beendeter Zugabe wurde noch 30 min bei 25 °C gerührt und anschliessend auf 110 °C erhitzt. Nach 4 h bei dieser Temperatur wurde die Reaktionslösung mit 200 ml Chlorbenzol verdünnt und auf 70-80 °C abgekühlt. Dann wurde die Reaktionslösung auf 600 ml eisgekühlte konzentrierte Salzsäure gegossen. Das Gemisch wurde filtriert und anschliessend die Phasen getrennt. Die wässrige Phase wurde noch einmal mit 100 ml Chlorbenzol extrahiert. Die vereinigten organischen Phasen wurden einmal mit 300 ml gesättigter Natriumhydrogencarbonatlösung gewaschen, über Natriumsulfat getrocknet und filtriert. Das Lösungsmittel wurde unter Vakuum abdestilliert und der so erhaltene Feststoff bei 50 °C/10 mbar für 24 h getrocknet. Man erhielt 54,0 g (93%) eines gelben Feststoffes, welcher nach Behandlung mit 3,0 g Aktivkohle aus Isopropanol/Wasser umkristallisiert wurde. Ausbeute: 41,8 g (72%) leicht gelbliche Kristalle.
13C NMR (CDCl3): δ = 145,69 (s); 139,20 (s); 132,59 (s); 129,12 (s); 128,67 (s); 127,74 (s); 127,23 (s); 118,91 (s); 110,98 (s).In 200 ml of chlorobenzene were dissolved at 25 ° C under nitrogen, 50 g (0.324 mol) of biphenyl. Subsequently, 51.88 g (0.389 mol) of anhydrous aluminum chloride were added and stirred for 15 min. At 20-25 ° C were then introduced 23.92 g (0.389 mol) of cyanogen chloride within one hour. After completion of the addition was stirred for 30 min at 25 ° C and then heated to 110 ° C. After 4 h at this temperature, the reaction solution was diluted with 200 ml of chlorobenzene and cooled to 70-80 ° C. Then, the reaction solution was poured onto 600 ml of ice-cooled concentrated hydrochloric acid. The mixture was filtered and then the phases were separated. The aqueous phase was extracted once more with 100 ml of chlorobenzene. The combined organic phases were washed once with 300 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and filtered. The solvent was distilled off under reduced pressure and the resulting solid dried at 50 ° C / 10 mbar for 24 h. This gave 54.0 g (93%) of a yellow solid, which was recrystallized after treatment with 3.0 g of activated carbon from isopropanol / water. Yield: 41.8 g (72%) of slightly yellowish crystals.
13 C NMR (CDCl 3): δ = 145.69 (s); 139.20 (s); 132.59 (s); 129.12 (s); 128.67 (s); 127.74 (s); 127.23 (s); 118.91 (s); 110.98 (s).
In 200 ml Chlorbenzol wurden bei 25 °C unter Stickstoff 50 g (0,324 mol) Biphenyl gelöst. Anschliessend wurden 51,88 g (0,389 mol) wasserfreies Aluminiumchlorid zugegeben und für 15 min gerührt. Bei 20-25 °C wurden darauf 23,92 g (0,389 mol) Chlorcyan innerhalb einer Stunde eingeleitet. Nach beendeter Zugabe wurde das Reaktionsgemisch noch 30 min bei 25°C gerührt und anschliessend auf 110 °C erhitzt. Nach 4 h bei dieser Temperatur wurde die Reaktionslösung mit 200 ml Chlorbenzol verdünnt und auf 70-80 °C abgekühlt. Dann wurden innerhalb von 30 min 40 ml Wasser zugetropft. Anschliessend wurde das Gemisch auf 20°C abgekühlt und die ausgefallenen Aluminiumsalze abfiltriert. Der Filterrückstand wurde noch zweimal mit je 100 ml Chlorbenzol gewaschen. Die vereinigten organischen Phasen wurden eingedampft und der so erhaltene Rückstand wurde bei 50 °C/10 mbar getrocknet. Man erhält 52,8 g (91 %) eines gelben Feststoffes, welcher laut GC 90,5% Biphenyl-4-carbonitril enthielt.In 200 ml of chlorobenzene were dissolved at 25 ° C under nitrogen, 50 g (0.324 mol) of biphenyl. Subsequently, 51.88 g (0.389 mol) of anhydrous aluminum chloride were added and stirred for 15 min. At 20-25 ° C were then introduced 23.92 g (0.389 mol) of cyanogen chloride within one hour. After completion of the addition, the reaction mixture was stirred for a further 30 min at 25 ° C and then heated to 110 ° C. After 4 h at this temperature, the reaction solution was diluted with 200 ml of chlorobenzene and cooled to 70-80 ° C. Then 40 ml of water were added dropwise within 30 min. Subsequently, the mixture was cooled to 20 ° C and the precipitated aluminum salts filtered off. The filter residue was washed twice with 100 ml of chlorobenzene. The The combined organic phases were evaporated and the residue thus obtained was dried at 50 ° C / 10 mbar. This gives 52.8 g (91%) of a yellow solid which according to GC 90.5% biphenyl-4-carbonitrile.
In 150 ml Chlorbenzol wurden bei 25 °C unter Stickstoff 51,88 g (0,389 mol) Aluminiumchlorid suspendiert. Anschliessend wurden innerhalb von 45 min 23,92 g (0,389 mol) Chlorcyan eingeleitet. Nach einer Nachreaktionszeit von 15 min wurde auf 90 °C erwärmt. Zur Suspension wurde dann innerhalb einer Stunde eine Lösung von 50 g (0,324 mol) Biphenyl in 50 ml Chlorbenzol zugetropft. Anschliessend wurde auf 110 °C gebracht und für 4 h reagieren gelassen. Dann wurde die Reaktionslösung innerhalb von einer Stunde auf 200 ml Wasser von 90 °C abgelassen. Man spülte das Reaktionsgefäss mit 100 ml Chlorbenzol nach und lies die Phasen separieren. Nach dem Ablassen der wässrigen Phase wurde die organische Phase bei 90 °C mit 200 ml Wasser gewaschen. Die so erhaltene organische Phase wurde anschliessend bei 40 °C mit 5 g Aktivkohle 30 min gerührt und dann filtriert. Anschliessend wurde die organische Phase zur Trockne eingedampft. Nach dem Trocknen bei 50 °C/10 mbar erhielt man 57,2 g (98,5%) eines gelben Feststoffes, welcher laut quantitativer 13C NMR-Analyse ca. 80% Biphenyl-4-carbonitril enthielt.51.88 g (0.389 mol) of aluminum chloride were suspended in 150 ml of chlorobenzene at 25.degree. C. under nitrogen. Subsequently, within 45 min 23.92 g (0.389 mol) of cyanogen chloride were introduced. After a post-reaction time of 15 min was heated to 90 ° C. To the suspension was then added dropwise within one hour a solution of 50 g (0.324 mol) of biphenyl in 50 ml of chlorobenzene. It was then brought to 110 ° C and allowed to react for 4 h. Then, the reaction solution was drained to 200 ml of water at 90 ° C in one hour. The reaction vessel was rinsed with 100 ml of chlorobenzene and the phases were separated. After draining the aqueous phase, the organic phase was washed at 90 ° C with 200 ml of water. The resulting organic phase was then stirred at 40 ° C with 5 g of activated carbon for 30 min and then filtered. Subsequently, the organic phase was evaporated to dryness. After drying at 50 ° C./10 mbar, 57.2 g (98.5%) of a yellow solid were obtained which, according to quantitative 13 C NMR analysis, contained about 80% of biphenyl-4-carbonitrile.
Claims (4)
- A process for preparing biphenyl-4-carbonitrile of the formula
- The process of claim 1, characterized in that the anhydrous aluminum chloride and the cyanogen chloride are each used in an amount of from 1.0 to 1.5 mol per 1 mol of biphenyl.
- The process of claim 1 or 2, characterized in that the reaction is carried out in a halogenated aromatic solvent.
- The process of claim 3, characterized in that the halogenated aromatic solvent used is chlorobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02783019A EP1442010B1 (en) | 2001-10-30 | 2002-10-28 | Method for the production of biphenyl-4-carbonitrile |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01125852 | 2001-10-30 | ||
| EP01125852 | 2001-10-30 | ||
| EP02783019A EP1442010B1 (en) | 2001-10-30 | 2002-10-28 | Method for the production of biphenyl-4-carbonitrile |
| PCT/EP2002/012008 WO2003037848A1 (en) | 2001-10-30 | 2002-10-28 | Method for the production of biphenyl-4-carbonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1442010A1 EP1442010A1 (en) | 2004-08-04 |
| EP1442010B1 true EP1442010B1 (en) | 2008-01-09 |
Family
ID=8179115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02783019A Expired - Lifetime EP1442010B1 (en) | 2001-10-30 | 2002-10-28 | Method for the production of biphenyl-4-carbonitrile |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7002034B2 (en) |
| EP (1) | EP1442010B1 (en) |
| AT (1) | ATE383333T1 (en) |
| DE (1) | DE50211531D1 (en) |
| WO (1) | WO2003037848A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230757B (en) * | 2013-07-26 | 2016-08-10 | 河北允升精细化工有限公司 | A kind of improved method of preparing 4-biphenylnitrile |
| CN118598772B (en) * | 2024-08-08 | 2024-11-26 | 内蒙古环圣科技有限公司 | Synthesis method of o-cyanophenol |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2737210C2 (en) * | 1977-08-18 | 1983-06-23 | Bayer Ag, 5090 Leverkusen | Process for the production of nitriles |
| AU694590B2 (en) * | 1994-11-24 | 1998-07-23 | Basf Aktiengesellschaft | Process for preparing halogenated methyl benzoyl cyanides |
| DE19833409A1 (en) * | 1997-08-14 | 1998-12-24 | Lonza Ag | 4-Cyano-4'-hydroxy-bi:phenyl preparation in high yield |
-
2002
- 2002-10-28 DE DE50211531T patent/DE50211531D1/en not_active Expired - Lifetime
- 2002-10-28 EP EP02783019A patent/EP1442010B1/en not_active Expired - Lifetime
- 2002-10-28 WO PCT/EP2002/012008 patent/WO2003037848A1/en active IP Right Grant
- 2002-10-28 US US10/493,979 patent/US7002034B2/en not_active Expired - Lifetime
- 2002-10-28 AT AT02783019T patent/ATE383333T1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| US20050085657A1 (en) | 2005-04-21 |
| US7002034B2 (en) | 2006-02-21 |
| WO2003037848A1 (en) | 2003-05-08 |
| DE50211531D1 (en) | 2008-02-21 |
| EP1442010A1 (en) | 2004-08-04 |
| ATE383333T1 (en) | 2008-01-15 |
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